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I am really glad you've resumed the group 3 dispute. I have indeed had the feeling that the previous disputes on the matter were not entirely complete---not just because I prefer your opinion as well, even though I actually do---because it seemed to me not all arguments had been taken in account equally. Thank you for dropping by; if your stay in our project lasts longer, please feel welcome.--
R8R (
talk)
04:12, 26 February 2018 (UTC)reply
Yellow colour of caesium
I wonder what happens for francium when relativistic effects should really be important. ^_^ If the transition involved is the ns–np one to the first excited state then we can look up the energy levels and see that the transition energy is closer to that of Rb than that of Cs, which would predict a silvery colour again; is that simplistic analysis correct?
Double sharp (
talk)
04:13, 8 April 2018 (UTC)reply
No, I didn't mean that the yellow colour of Cs is related to relativistic effects; the plasmonic frequency of Cs (going into the visible range) quite nicely continues the trend down the group (10.1103/PhysRev.44.353), and relativistic effects shouldn't be that big around Z ~ 50 (they're not big for Ag either, which is silvery). I was asking for Fr, for which relativistic effects should really be important. ^_^
Double sharp (
talk)
10:07, 8 April 2018 (UTC)reply
@
Double sharp:ns–np gap should increase for Fr compared to Cs, but I think that's not about the colour. The plasmonic frequency for Fr metal could be right on the edge of visible spectrum, making it pale yellow.
Droog Andrey (
talk)
03:59, 9 April 2018 (UTC)reply
Interesting (and perhaps coincidentally not too different from what the ns–np gap explanation would have us guess, which interpolating between Rb and Cs at least leaves the possibility of a pale yellow colour open). Do you know where I can find values for the plasmonic frequencies of the rest of the metals?
Double sharp (
talk)
04:04, 9 April 2018 (UTC)reply
I thought it might have been that, but initially dismissed that due to some differences, like for cerium (which is quite small in the paper). Is that one because your table is using its trivalent rather than tetravalent radius?
Double sharp (
talk)
09:31, 13 April 2018 (UTC)reply
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Is there much hope for getting Zn, Cd, and Hg in oxidation states above +2? I know
Zn(AuF6)3 has been suggested, but it may be thermochemically unstable and not really Zn(III) anyway (10.1021/ja3052409).
Double sharp (
talk)
12:17, 7 April 2020 (UTC)reply
@
Double sharp: EN for He will be updated, of course. As for metallicity, I'd rather wait for more computations. My intuition suggests that Og should be a metal; still have no idea for Cn.
Droog Andrey (
talk)
17:14, 21 July 2020 (UTC)reply
Fair enough. The superheavies are weird, I will wait. For now my userpage periodic table calls Cn and Og nonmetals since I have not enough chemical intuition for these, but as more computations come I will change it,
Since we are talking about metallicity again; I understand that antimony is normally classified as a metal in Russian schoolbooks, and that you have made some changes to your poster in the past to avoid conflict with them (i.e. not calling Cu2+ amphoteric). (For that reason I don't expect to see helium over beryllium any time soon; fixing group 3 is way more important for consistency. ^_^) Now, I understand that for that one there are obviously also chemical reasons, as the formation of [Cu(OH)42− has more to do with complex formation than acidity. So I wanted to ask it this way: if you were writing it for yourself without such a constraint, would you rather call antimony a metal or a nonmetal?
I currently think the fact that its chemistry seems on the border means that calling in the physical fact that it isn't a true metal may not be so bad. OTOH, mostly Sb alloys are metallic in conductivity, that is also something. If we exclude Sb from metals, the metal-nonmetal line goes forward by one when there's no contraction (Be to Al, Ga to Sn), stays put when there is one (Al to Ga), goes forward two for the first row when we lose both kainosymmetry and instantly gain significant shielding, and then runs away almost to the end in period 6 due to 6p3/2 expansion. Cationic chemistry seems a bit orthogonal to the idea; after all rhenium is a metal, no one doubts it even with less real aqueous cations than antimony, so it is not necessary, and if Ge2+ really exists then it is not even sufficient. But I don't know how much is best to weight these things.
Double sharp (
talk)
09:28, 22 July 2020 (UTC)reply
Wow, I didn't know beryllium had semimetallic properties. That is cool indeed. I suppose Be is maybe a bit more clearly on the metallic side chemically than Sb, but indeed I'd rather keep criteria to a minimum.
Just one more question before I maybe take a break from these issues then. ;) Regarding how I used to show "weak nonmetals" {H, B, C, Si, P, Ge, As, Se, Te}, "strong nonmetals" {N, O, F, S, Cl, Br, I}, "noble nonmetals" {He, Ne, Ar, Kr, Xe, Rn} (let's ignore period 7 for this): do you think this sort of thing is a useful generalisation attempt? I mostly was inspired by Gary Wulfsberg's Principles of Descriptive Inorganic Chemistry for it, but as you noted it's not just electronegativity, there is also oxidising power, electron affinity, and the physical metal-nonmetal distinction. And do you think there's anything in trying to extend this combination of properties to metal-nonmetal dichotomy and maybe to separate stronger and weaker classes of metallic elements, or is it better to treat the metals vs nonmetals topic in the physical way mostly only?
Double sharp (
talk)
14:25, 24 July 2020 (UTC)reply
Never mind, I think I answered my own question. Metal-nonmetal difference seems more a simple substances thing than an element thing. ^_^
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In conjunction with your next update of helium EN to 3.20, I think a few atomic weights may need
updates to latest IUPAC values. Also, IUPAC now gives intervals for atomic weights of some elements. Where only a single value is needed,
they give conventional values with few significant figures. That would suggest the following changes (I guess 6 s.f. are used when more are known):
Germanium: 72.630 (maybe last figure can be dropped, ±0.008 uncertainty)
Selenium: 78.971 (maybe last figure can be dropped, ±0.008 uncertainty)
Molybdenum: 95.95
Technetium: better 97, since
NUBASE2016 says Tc-97 is a bit more stable than Tc-98
Cadmium: 112.414
Ytterbium: 173.045 (but this is ±0.010, so maybe should round off)
Mercury: 200.592
Thallium: 204.38
Seaborgium: better 269, this isotope is more stable (10.1103/PhysRevC.97.014320) with half-life 14+10 −4 minutes compared to 2.4 min for 271
Bohrium: better 270, more stable than 274 per NUBASE2016
Moscovium: better 290 per NUBASE2016
I don't mention cases where last figure accords but has some uncertainty. ;) And maybe I have not the latest atomic data for this, this is just latest I have.
Double sharp (
talk)
13:16, 14 August 2020 (UTC)reply
Ah, I see. Take your time, please, there's no rush. Just please do tell me when the corrected version is up, as I like having your table to link to. ;)
I guess this way it will be hard to put 119 up when
it hopefully comes next year. Or do you still plan to ignore it and the next ones for a while as I think you said the last time? Maybe that's a shame, as following something
R8R said back in 2018, 119 would not really be less worthy than Og.
If you are all right (which I hope you are), there is a little question I have wondered about in passing and forgot to ever ask.
What states of matter do you think the 7th period elements should be in at standard conditions? (Or "close enough" since Cs and Ga have melted by 30°C.) I ask because lots of periodic tables I remember having seen IRL "cop out" and classify solid/liquid/gas/synthetic(!), which seems a bit lame to me.
I admit my first instinct was to colour Fr, Cn, Fl liquid (along with Hg, Cs, Ga) and leave the rest solid (I don't think oddities like the Ga structure would recur, but you never know, maybe for Ts), but I confess I don't know enough to answer it well and therefore ask you. ;)
Double sharp (
talk)
09:14, 18 August 2020 (UTC)reply
Thank you! I suppose for Fr it is due to 7s contraction? Out of curiosity (and of course a desire to learn more) I'd like to know how you got the estimate for Ts. ;)
Double sharp (
talk)
03:03, 20 August 2020 (UTC)reply
Again, thank you! I see there are polarisability values for everybody but Lv at 10.1080/00268976.2018.1535143. So, higher polarisability strengthens metallic bonding? Makes sense to my high-school intuition (greater electrostatic attraction, but obviously not so much that delocalisation itself gets hard, which maybe affects f elements), although no doubt it is really more complicated. Maybe there is after all a good explanation for the melting points in group 2 that
Chemguide threw its hands up in the air for. XD
Double sharp (
talk)
07:21, 20 August 2020 (UTC)reply
Polarizability itself does not strengthen metallic bonding. After all, metallic bonding strength affects boiling points, not melting ones. Polarizability of Ts matters if we suppose diatomic structure analogous to gallium or iodine. If metallic Ts is just fcc, then its melting point is even higher.
Droog Andrey (
talk)
07:02, 21 August 2020 (UTC)reply
I see, thank you for the explanation. Now indeed kicking myself for forgetting the basic high-school knowledge that metallic bond only fully breaks at boiling, not melting. XD
I hope you do not mind my questions, because I want my understanding to be as correct as possible. So, how does melting Ga work exactly? Is it more or less like iodine where it is just about overcoming weaker interactions between Ga2 molecules, or is that a too naïve view? And is there a way to guess melting points from the structure of a metal?
Double sharp (
talk)
07:12, 21 August 2020 (UTC)reply
It's very non-trivial to guess melting points in general case. For Ga the key might be interaction strengthening in more dense liquid state (you see, electrical resistance falls upon melting).
Droog Andrey (
talk)
09:16, 21 August 2020 (UTC)reply
Gotta add
Sigma-Aldrich to the list of periodic table makers that made the wrong decision on Fr. Although since atomic radius of Fr is between Cs and Rb (which melts at 39°C), I guess they might get away with claiming that they had a really hot "room temperature" in mind. ;)
Double sharp (
talk)
12:33, 1 March 2021 (UTC)reply
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Paper (containing calculations for the E140 isoelectronic sequence). Seems like indeed we transition from open-shell 5g at 1422+, to closed-shell at 1433+. From 1433+ on, configuration we get is closed shell [Og]8s25g188p2. Since 8p should not be drowned yet at the start, maybe we get two-too-high oxidation states compared to the actinoid congeners then?
Double sharp (
talk)
09:50, 18 February 2021 (UTC)reply
Do you think the 2×18 footnote is better, or the form we currently have with 143–156 assigned to an f series because of the g subshells presumably being last active at 142?
If I read and understand your
older popularisation article correctly, we should probably have 121–124 acting like first four actinoids (maybe more active still), followed by a bunch of copycats of uranium-like behaviour as the 5g fills underneath. Perhaps with +4 becoming more important than +6 as 8s2 falls into the core later in this series, and then rising again for 143++, before 8p1/2 also sinks into core at 150-ish and we start to see same fall as late actinoids. But how good, say, do you think would be homologies between things like 121 and 139 (from top row to bottom?).
Double sharp (
talk)
08:13, 25 February 2021 (UTC)reply
Huh, apparently some new calculations got published for Cn:
[1]. Again predicting a dispersion-bound noble liquid, and also claiming that 6d > 7s order suppresses metallic bonding. (Which I don't get, admittedly as a layman here. Shouldn't 6d expansion rather favour metallic bonding? Early 6d metals like Sg surely have 6d > 7s order too. How far away is 7p1/2, too; could it play a role?)
I must admit, I'm surprised at large liquid range calculated for a supposedly dispersion-bounded solid in the new work (PBE-D3, mp −47°C, bp 88°C). With PBEsol (which they say is better suited for metallic systems) the range is smaller (mp 11°C, bp 67°C), but still seems large for me (just as a layman here) comparing with Rn (mp −71 °C, bp −62 °C). However it does seem intermediate between Rn and Hg (mp −39 °C, bp 357 °C) in a way I could get behind. Are the extra electrons and relativity that effective? Well, they agree Fl is a metal (same paper, citing
this older one), with predicted mp −73°C (lower than Cn!), bp 107°C (though they say to take it with a grain of salt). Interestingly similar to what you wrote at the end of
this old section, with Cn barely more volatile than Hg, and Fl well more volatile but still a liquid. They both seem somehow "on the way" on the transition from dispersion forces to metallic bonding, with Cn closer to Rn and Fl closer to Hg. ;)
Though my high-school chemical intuition still wonders if, even if Cn might be dispersion-bounded, it might not be pushed to engage in metallic interactions when alloyed with somebody else as suggested by Eichler
here. ;)
Double sharp (
talk)
09:42, 1 March 2021 (UTC)reply
Hi, do you have a source for what you wrote on
your website "например, хром долгое время считался одним из самых твёрдых металлов, но, когда его научились глубоко очищать, обнаружилось, что хром пластичен"? It really would be something amazing to point out when whistle-stop describing metals. ;)
Double sharp (
talk)
04:08, 7 March 2021 (UTC)reply
I think I remember you saying that Sb chemically is pretty much on the edge between metals and nonmetals. So I want to ask you where you think At is. ;)
Double sharp (
talk)
06:55, 19 March 2021 (UTC)reply
Regarding amorphous metals: seems by
doi:
10.1016/0022-3093(93)90768-S that amorphous Sb is only a semiconductor (while Bi is a metal), but that by constraining it to match Bi short-range structure amorphous Sb can be metallised anyway. Still kinda OK for the weak metal, I guess?
Hi DA, I have a couple of questions about something you wrote
in 2018:
What did you mean about the reverberation of secondary periodicity from Na to K? (Is it because Li is above a 1s2 core whereas the other ones are above an ns2np6 core which shields a bit worse?
This is the only thing I could find, pages 17 through 19. I admit that trend H-Li-Na-K, He-Be-Mg-Ca in electronegativity seems somehow to have similarity to F-Cl-Br-I or Ne-Ar-Kr-Xe, maybe the more so in those cases with reversed electronegativity order where Li becomes more electropositive than Na.)
What criterion would you use to decide the fate of s-elements, since it is the only block for which the idea "look at highest angular momentum subshell" does not work? (Myself, I would take the cases "one valence electron" and "two valence electrons" separately as you suggest, but seeking some confirmation XD.)
K has much larger core, and therefore higher polarizability than Na. The same occurs for Cs and Rb. So we have electropositivity jumps from odd to even period for s-elements. And, yes, I'd rather choose "≤ 2 valence electrons" for s-elements :)
Droog Andrey (
talk)
11:49, 3 April 2021 (UTC)reply
Huh, that's cool. Didn't know that, thanks. Why does it happen? Just comparing the previous noble gases, I see that He is tiny, Ne is a bit less tiny but not too much larger, and then suddenly Ar is a lot larger. Sort of suggests to me lack of kainosymmetry from Ar onwards, but then what's going on for Kr vs Xe? The 3d contraction hurting Kr maybe? I'd guess what is correct for He through Xe series should also be correct for Li+ through Cs+ series. XD
Is electropositivity meant in the sense I know from high school (opposite of electronegativity), or something a bit different? Because on your scale series H–Cs and He–Ba are monotonic electronegativity decreases.
So it seems to me that even periods in s block behave as odd periods in other blocks and vice versa. Seems maybe an argument for
Janet table, isn't it LOL. Particularly so if 3d contraction is responsible for size not going up so much between K+ and Rb+. XD (Not being very serious here, since the big energy gap (n−1)p << ns seems like a much more relevant argument.)
Will 7p elements be a problem? 7s is a bit doubtfully valent for flerovium, isn't it? I don't think we can really speak of Fl through Og as 4 through 8 valence electrons. Are we just going to just take ns2 npx at its word? Subtracting 2 from column numbers might work to account for preemptive filling of s orbitals in each case, except I'm not sure 7p1/2 is actually valent at Ts and Og. Or maybe just ignore spin-orbit problem, LOL. XD
Well, I guess I could answer this to my satisfaction mostly: big energy gap (n-1)p << ns is more important than weak s-block secondary periodicity, because it gives chemically important noble-gas situation. So, easier to just remember that s-block really represents the previous n+l value; it was an exception for preemptive ns2 filling, so it can be an exception for even-odd rule too. :) As for superheavies: classification is basically partly done for pragmatism (just like how in mathematics it was eventually decided not to call units primes mostly), so a slight approximation is allowable. They are also exceptions to even-odd rule, but for the most part noble gas configuration still exists as a thing (I mean, maybe Uue can breach the shell for some oxidising compounds, but that should really be it I think).
Double sharp (
talk)
06:34, 12 April 2021 (UTC)reply
Just curious: predictions in WP articles are given as (Pauling) 0.86 for Uue, 0.91 for Ubn. Do you find that plausible? (It would put Uue as less electropositive than K, but Ubn as between Sr and Ba. Well maybe, given reversal seems to hit Fr more than Ra...)
Hmm, not too different from
Karol's I see. Of course his values for 7p are not interesting because 7s is hardly valent there, but maybe the 8s values are less bad I guess.
Double sharp (
talk)
09:59, 13 April 2021 (UTC)reply
OK, somewhat disappointingly the predictions seem to still fall into a black hole after Ubn. I think I would guess something like (on your scale) Uue 0.82, Ubn 0.93, Ubu 0.96, Ubb 0.99 maybe to start the eighth row. After that, probably massive collision among all the other assigned ones in 4f and 5f. Dunno if the usual half-row situation (like Mn/Zn, Eu/Yb) would do anything at Ube at this point; I guess 8th row blocks should be too blurred to make much difference.
Double sharp (
talk)
11:44, 13 April 2021 (UTC)reply
I'd say the chemistry of antimony is right on the edge between metallic and nonmetallic. I'd even say that there's some kind of parallel between Sb and Re (both are just before the middle of the block). Yes, white phosphorus is metastable as well as diamond, for example, but they are both much more stable than black antimony.
”
So, just curious re what parallels between Sb and Re you meant. :)
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Although recently published
experiments now say it's probably a volatile metal (
metallic interpretation, because a noble gas would not deposit on Au at room temperature). Seems like Cn and Fl metallicity are both highly underestimated by calculations compared to experiments, and I wonder why. (I thought it might have been 7p SO splitting being bigger than thought, but while that would indeed make Cn more metallic, it'd make Fl less so, so that doesn't work.)
Double sharp (
talk)
23:02, 9 October 2022 (UTC)reply
It's quite difficult to calculate metallicity. Chemical intuition suggests that Cn and Fl should be volatile metals indeed. However, I'd expect Cn a bit more volatile than Fl :)
Droog Andrey (
talk)
08:02, 10 October 2022 (UTC)reply
I'd like to see them! I know many are in
Grochala (2018) and
Kurushkin (2020). I haven't been able to find a copy of
Henry Bent's book, but his daughter
wrote an article. But I'd really like to find more differences between He and heavier noble gases. I have wondered if superfluid/supersolid phenomena for He are related to the spherical 1s. (I mean, obviously Ne is solid at the relevant temperatures, which is why looking at supersolids might be more fruitful.)
To me, the definitive argument is the way Scerri referred to QM in this article. The PT is an expression of the quantum-mechanical laws, not the final chemistry that is many steps removed from it. So not even Ptolemy vs Copernicus, but Ptolemy vs Newton, in a sense.
What do you think of Scerri's support for the Janet (fdps) table with the s-block on the right edge? My general impression is that within-block trends look better with Janet (fdps) because then ℓ changes monotonically and first-row anomaly / secondary periodicity consistently follows the n+ℓ parity difference (including s-block directly for 1s vs 2s, and in the sense of cores and thus polarisability for 3s vs 4s and 5s vs 6s); but between-block trends across the period look better with the standard sfdp because the energies of ns orbitals
are closer to those of the next n+ℓ group, so the natural trend (e.g. atomic radius) goes from group 1 to group 18. Relativistic shrinking of np3/2-(n+1)s gap would muddy that for the period divide from Og to 119, e.g.
7p-8s hybridisation in LvH2, but I think that is too weak a reason. But maybe one should just think of the PT as a spiral (to preserve the increasing Z order), and just view fdps and sfdp as cutting it in two different places.
Double sharp (
talk)
19:11, 17 November 2022 (UTC)reply
It's kind of old, but
Jensen wrote a pretty good article on periodicity for Britannica On-Line 2000. (Though his opinion then was that Zn, Cd, and Hg don't use d-orbitals, and I'd argue there are problems with his treatment of the s-block. Not sure what he thinks now. I'd say my preferred approach is an update of this, recognising valent d-orbitals in group 12, and accepting that valence manifolds change down the s-block e.g. adding p from He to Be, or d from Mg to Ca, and asking for only the same number of valence electrons. Basically like what I've previously discussed with you.)
Double sharp (
talk)
12:33, 9 December 2022 (UTC)reply
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If the Cs species are metastable, but the ionisation energies make them unrealistic, then I wonder if they might be prepared by β− decay of Xe fluorides or oxides.
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